Aqueous electronic circuit assembly cleaner and method

ABSTRACT

The present invention relates to environmentally safe aqueous saponifier compositions for cleaning electronic circuit assemblies, such as printed circuit or printed wiring boards, during their fabrication. Alkali metal carbonate and bicarbonate salts are utilized preferably with various adjuvants, such as an antifoam agent or surfactant to achieve a variety of objectives, among which are the removal of solder flux, oils, waxes, and greasy substances and adhesive and other residues.

RELATED APPLICATION

This application is a Continuation-in-part of U.S. Ser. No. 731,512,filed Jul. 17, 1991, now abandoned.

FIELD OF THE INVENTION

The present invention relates to environmentally safe aqueous saponifiercompositions for cleaning electronic circuit assemblies, such as printedcircuit or printed wiring boards, during their fabrication. Alkali metalcarbonate and bicarbonate salts are utilized preferably with variousadjuvants, such as a reducing agent or antifoam agent, to achieve avariety of objectives, among which are the removal of solder flux, oils,waxes and greasy substances and adhesive and other residues.

BACKGROUND OF THE INVENTION

The cleanliness of electronic circuit assemblies (ECA), such as printedcircuit boards (PCB) or printed wiring boards (PWB), is generallyregarded as being critical to their functional reliability. Ionic andnonionic contamination on circuit assemblies is believed to contributeto premature failures of the circuit assemblies by allowing shortcircuits to develop.

In the manufacture of electronic circuit assemblies, ionic and nonioniccontamination can accumulate after one or more steps of the process.Circuit assembly materials are plated, etched, handled by operators inassembly, coated with corrosive or potentially corrosive fluxes andfinally soldered.

In the fabrication of electronic circuit assemblies, e.g. printedcircuit boards soldering fluxes are first applied to the substrate boardmaterial to ensure firm, uniform bonding of the solder. These solderingfluxes fall into two broad categories: rosin and non-rosin, or watersoluble, fluxes. The rosin fluxes, which are generally non-corrosive andhave a much longer history of use, are still widely used throughout theelectronics industry. The water soluble fluxes, which are a more recentdevelopment, are being used increasingly in consumer productsapplications. Because they contain strong acids and/or aminehydrohalides and are thus corrosive, the water soluble soldering fluxescan cause circuit failure if residual traces of the material are notcarefully removed. For that reason military specifications require theuse of rosin fluxes.

Even the use of rosin soldering fluxes, however, can lead to prematurecircuit failure due to decreased board resistance if traces of residualflux are not removed following soldering. While water soluble fluxes canbe easily removed with warm, soapy water, the removal of rosin flux fromprinted circuit boards has traditionally been carried out with the useof chlorinated hydrocarbon solvents such as 1,1,1,-trichlorethane,trichloromonofluoromethane, methylene chloride,trichlorotrifluoroethane, or mixtures or azeotropes of these solvents.These solvents are undesirable, however, because they are toxic. Thus,their use is subject to close scrutiny by the Occupational Safety andHealth Administration (OSHA), and stringent containment equipment mustbe used. Moreover, if released into the environment these solvents arenot readily biodegradable and are thus hazardous for long periods oftime.

Alkaline cleaning compounds known as the alkanolamines, usually in theform of monoethanolamine, have been used for rosin flux removal as analternative to the toxic chlorinated hydrocarbon solvents. These high pHcompounds (e.g., about 12 pH), chemically react with rosin flux to forma rosin soap through the process of saponification. Other organicsubstances such as surfactants or alcohol derivatives may be added tothese alkaline cleaning compounds to facilitate the removal of suchrosin soap. Unfortunately, these compounds, as the water solublesoldering fluxes, have a tendency to cause corrosion on the surfaces andinterfaces of printed wiring boards if they are not completely andrapidly removed during the fabrication process.

In other approaches, Daley et al., U.S. Pat. No. 4,635,666 utilize ahighly caustic solution having a pH of 13 in a batch cleaning process.This method severely oxidizes the solder applied to the circuit board.In Hayes et al., U.S. Pat. Nos. 4,640,719 and 4,740,247 rosin solderingflux and other residues are removed from electronic assemblies by meansof terpene compounds in combination with terpene emulsifying surfactantsby rinsing in water.

The complete removal of adhesive and other residues also poses aproblem. During the manufacture of electronic circuit assemblies thecomponents are mounted on the upper surface of the board with leadsprotruding downwardly through holes in the board and are secured to thebottom surface of the board by means of an adhesive. Further, it issometimes necessary to temporarily protect certain portions of the boardfrom processing steps such as the process of creating corrosionresistant gold connecting tabs at the board edges. This transientprotection of portions of the circuit board can be achieved by theapplication of special adhesive tape to susceptible areas. Once suchprotection is no longer needed, the adhesive tape must be removed. Inboth instances, a residue of adhesive generally remains which, if notthoroughly removed, can cause premature board failure. Removal of thisadhesive residue has traditionally been carried out by the use ofchlorinated solvents which, as already described, are toxic andenvironmentally undesirable.

Thus, the residual contaminants which are likely to be found onelectronic circuit assemblies and which can be removed by thecompositions and method of the present invention include, but are notlimited to, for example, rosin flux, photoresist, solder masks,adhesives, machine oils, greases, silicones, lanolin, mold release,polyglycols and plasticizers.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide compositions andmethods for the safe and effective removal of rosin soldering fluxesfrom electronic circuit assemblies, e.g., printed circuit boards,without otherwise adversely affecting the boards. It is a furtherobjective of this invention to provide safe and effective compositionsand methods for the removal of other residual contaminants from printedcircuit assemblies.

This invention provides cleaning compositions and methods for theremoval of rosin solder fluxes and other residues during the fabricationof printed circuit or wiring boards. As a result, the possibility ofpremature circuit failure that might occur in the absence of suchcleaning is eliminated or greatly reduced. The cleaning efficacy of thecompositions of the invention is such that printed wiring boards thustreated meet stringent U.S. Department of Defense specifications.

The compositions of the invention are characterized by non-corrosivenessand low environmental impact, unlike the chlorinated hydrocarbonsolvents and alkaline cleaners that have heretofore been employed forprinted wiring board and printed circuit board cleaning. Advantageously,the saponifier compositions, as used herein, exhibit biological oxygendemands (BOD) and chemical oxygen demands (COD) well below the limitspromulgated by various governmental environmental agencies For example,BODs considerably below 200 ppm, e.g., 35 and CODs considerably below1000 ppm, e.g., 71 ppm are regularly attained. As a result, the need forcostly containment equipment is eliminated. Further, the problem ofcostly waste treatment, e.g., processing and disposal steps, is notencountered.

The present invention provides printed circuit/wiring board cleaningcompositions comprising alkali metal carbonate and bicarbonatesaponifier salts so combined that they have, when used in concentrationsof about 1 to 15 percent by weight, a pH of from about 10, or less, to12 and an adequate reserve of titratable alkalinity, at least equivalentto from about 0.3 to 4.5 percent caustic potash (potassium hydroxide),when titrated to the colorless phenolphthalein end point, which is aboutpH 8.4. At least about 50 percent and, preferably, at least about 65percent by weight of the carbonate salts comprise potassium carbonate.The aqueous saponifier solutions generally contain from about 1 to 15percent or even more depending on the particular conditions and,preferably, from about 2 to 8 percent by weight of the salts comprisingthe saponifier composition. In addition, the saponifier solutionsusually contain a small amount, e.g., from about 50 to 5000 ppm of awater soluble reducing agent (oxygen scavenger). Preferably, thesaponifier solutions also contain at use a small amount, e.g., up toabout 0.1 percent by weight of an antifoam agent. These, as well asother adjuvants, e.g., wetting agents, surfactants, etc., can beincluded with the salts per se or in any solution thereof no matter whatthe concentration of salts therein. When used according to the above,the compositions do not leave an undesirable residual film.

BRIEF DESCRIPTION OF THE FIGURES

The efficacy of this invention will be better understood by reference toFIGS. 1-7 herein wherein the test results of certain embodiments of thesaponifiers of this invention are illustrated.

FIGS. 1, 2, 4, and 6 represent typical curves showing the cleaningefficiences of various concentrations of saponifier solutions resultingfrom visual testing as described herein.

FIGS. 3, 5, and 7 represent typical curves showing the cleaningefficiences of various concentrations of saponifier solutions resultingfrom equilibrium resistivity measurements as described herein.

DETAILED DESCRIPTION OF THE INVENTION

The objects and advantages mentioned above as well as other objects andadvantages may be achieved by the compositions and methods hereinafterdescribed.

Essentially, the saponifier compositions of the invention aresubstantially water soluble and comprise mixtures of certain alkalimetal salts. Accordingly, the term "saponifier compositions" as usedherein is intended to define the mixture of essentially dry ingredientscomprised of the alkali metal salts and, if desired, any added adjuvantsas hereinlater described.

As hereinlater set forth, the saponifier compositions may be dilutedinto concentrated solutions. The terms "saponifier concentratedsolutions" or "concentrates" as used herein define aqueous mixturescontaining from about 10 to 45 or more percent by weight of the drysaponifier compositions with the balance being essentially water.

As used herein the terms "saponifier solutions" or "saponifier solutionsin use" is meant to define aqueous mixtures of from about 1 to 15percent by weight of the dry saponifier composition with the balancecomprised essentially of water which are employed in the cleaningmethods of the invention. Preferably deionized water is used for boththe saponifier concentrates and saponifier solutions.

In accordance with the invention, additives, adjuvants, or the like, maybe included with the saponifier compositions, saponifier concentrates,or the saponifier solutions in use. Such additives, adjuvants, and thelike should be water soluble or at least readily water dispensible.

The saponifier compositions of the present invention contain mixtures ofalkali metal salts, i.e., mixtures of carbonates and bicarbonates. Thealkali metals contemplated include potassium, sodium and lithium, withpotassium being preferred. The carbonate salts include potassiumcarbonate, potassium carbonate dihydrate, and potassium carbonatetrihydrate, sodium carbonate, sodium carbonate decahydrate, sodiumcarbonate heptahydrate, sodium carbonate monohydrate, sodiumsesquicarbonate and the double salts and mixtures thereof. Thebicarbonate salts include potassium bicarbonate, sodium bicarbonate,lithium bicarbonate and mixtures thereof. Generally, the saponifiercompositions of the invention will contain the carbonate salts inamounts of from about 70 to 95 percent, preferably, about 82.5 to 92.5percent, for example, about 87.5 percent by weight. The carbonate saltscomprise at least about 50 percent, preferably at least about 65percent, for example, about 75 percent by weight of potassium carbonate.The bicarbonate salts in amounts of about 5 to 30 percent, preferably,about 10.0 to 20.0 percent, for example, about 12.5 percent by weight,based on the total amount of the carbonate and bicarbonate saltsutilized. As set forth above, the alkali metal carbonate and bicarbonatesalts are utilized in combinations and in concentrations such that theresultant solutions have a pH of from about 10, or somewhat less, to 12and also an adequate reserve of titratable alkalinity, as leastequivalent to from about 0.3 to 4.5%, preferably from about 0.6 to 4.5%,caustic potash (potassium hydroxide), when titrated to the colorlessphenolphthalein end point, which is at about pH 8.4.

The saponifier compositions of the present invention which are comprisedof carbonate and bicarbonate salts as set forth above are generallyprepared as aqueous concentrates. Such aqueous saponifier concentratesmay contain from about 10 up to about 45, or more, percent by weight ofthe salts depending on their solubility in water. Preferably, theconcentrates contain about 15 to 40 percent by weight of the saponifiercomposition (i.e., carbonate and bicarbonate salts) with the remainderessentially water. The dilutions of these concentrates are determined bymanufacturing, packaging, shipping, storage, and other factors. Itshould be understood that the amount of solute in these concentrates isnot especially critical.

The saponifier solutions which are employed in the cleaning proceduresdescribed herein usually contain from about 1 to 15, or more, percentand, preferably, from about 1.7 to 8 percent by weight of the saponifiercompositions of this invention with the balance being essentially water.The upper limit of concentration of the saponifier composition is notcritical and is determined by fabrication conditions, the amount ofresidues and the difficulty of removing same from the circuitassemblies, etc. The adjuvants, additives, and the like which may bealso employed are used in such small amounts relative to the othercomponents that they need not be included when defining the weightpercentages of the saponifier concentrates or the saponifier solutionsas described and used herein.

In accordance with the invention, at least one water-soluble reducingagent and/or antioxidant is preferably employed. The reducing agentsinclude, alone or in combination, sodium bisulfite and hydrazinehydrate, which are the preferred reducing agents, the aminoboranes,e.g., dimethylamine borane, the alkali-metal borohydrides, e.g.,potassium borohydride, the alkali-metal hydrophosphites andhydrosulfites, e.g., sodium hydrosulfite, and formalin. Other preferredreducing agents include dihydrazine sulfate and other salts thereof.

The reducing agent employed may also be an hydroxylamide, or anhydroxylamine addition salt, e.g., hydroxylamine sulfate, hydroxylaminehydrochloride, hydroxylamine nitrate, hydroxylamine acetate,hydroxylamine formate, hydroxylamine bromide, and the like, and mixturesthereof. Other salts such as potassium pyrosulfate, sodiumhypophosphite, sodium and potassium sulfite, sodium bisulfite, sodiummetabisulfite, sodium dithionite, sodium formaldehyde sulfoxylate, zincformaldehyde sulfoxylate, sodium nitrite, and mixtures thereof can alsobe used.

The water soluble reducing agent is supplied in an amount which issufficient to substantially, if not completely, preclude the oxidationof solder to its "dull" state and maintain it in its "shiny" state whichis deemed important to assess the adequacy of the soldered joints orconnections. The concentration of the reducing agent with the saponifiershould be an effective amount which will generally range from about 50to 5000 ppm, preferably, about 100 to 1000 ppm, of the total aqueoussaponifier solution in use. Amounts included in the saponifiercompositions and concentrates can be calculated accordingly.

The antioxidants which maybe employed in accordance with the inventioninclude butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT),terbutyl hydroquinone (TBHQ), the tocopherols, and the like. Generallythe antioxidants are employed in amounts such that the saponifiersolution contains from about 10 to 1000 ppm and, preferably, from about50 to 500 ppm, of the aqueous saponifier solution in use.

At least one antifoam agent may be, and preferably is, included in anyof the saponifier products of this invention. The antifoam agent isutilized to alter the surface tension caused by the rosinflux/saponifier combination and prevent foam or detrimental residual"film" from being formed. Desirably, the agent will produce a surfacefilm on the component that has a substantially constant surface tensionwhen subjected to expansion or contraction. The foam inhibitors hereinmust do this by swamping the surface with nonfoaming, rapidly diffusing,non-cohesive, only moderately surface-active molecules, so that anytransient rise in surface tension caused by film expansion is rapidlynegated. It is important, if not critical, that the antifoam agent usedherein does not act by replacing the flux/saponifier film with anotherresidual surface film, e.g., with a film of soap molecules that form a"solid," brittle film.

Preferred examples of antifoam agents include compounds formed bycondensing ethylene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol. The hydrophobicportion of the molecule which exhibits water insolubility has amolecular weight of from about 1,500 to 1,800. The addition ofpolyoxyethylene radicals to this hydrophobic portion tends to increasethe water solubility of the molecule as a whole and the liquid characterof the product is retained up to the point where polyoxyethylene contentis about 50 percent of the total weight of the condensation product.Examples of such compositions are the "Pluronics" sold byBASF-Wyandotte.

Other suitable antifoam agents include: the polyethylene oxidecondensates of alkyl phenols, e.g., the condensation products of alkylphenols having an alkyl group containing from about 6 to 12 carbon atomsin either a straight chain or branched chain configuration, withethylene oxide, the said ethylene oxide being present in amounts equalto 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkylsubstituent in such compounds may be derived from polymerized propylene,diisobutylene, octene, or nonene, for example.

Also suitable are those derived from the condensation of ethylene oxidewith the product resulting from the reaction of propylene oxide andethylene-diamine or from the product of the reaction of a fatty acidwith sugar, starch or cellulose. For example, compounds containing fromabout 40 percent to about 80 percent polyoxyethylene by weight andhaving a molecular weight of from about 5,000 to about 11,000 resultingfrom the reaction of ethylene oxide groups with a hydrophobic baseconstituted of the reaction product of ethylene diamine and excesspropylene oxide, and hydrophobic bases having a molecular weight of theorder of 2,500 to 3,000 are satisfactory.

In addition, the condensation product of aliphatic alcohols having from8 to 18 carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide, e.g., a coconut alcohol-ethyleneoxide condensate having from 10 to 30 moles of ethylene oxide per moleof coconut alcohol, the coconut alcohol fraction having from 10 to 14carbon atoms, may also be employed.

The antifoam agents of the present invention are preferably employed inthe saponifier solution in amounts of up to about 0.1 percent by weight,preferably, about 0.01 to 0.05 percent by weight based on the totalweight of the aqueous saponifier solution. The antifoam agents can alsobe included in the dry saponifier compositions as well as the saponifierconcentrates so as to result in the desired concentrations at use.

The present invention also contemplates the use of one or moresurfactants in the saponifier solutions in order to enhance the wettingability of the saponifier and permit maximum penetration thereof withinregions of the circuit boards most difficult to clean. Suitable wettingagents include anionic, nonionic and cationic surfactants (orcombinations thereof such as amphoteric surfactants). The surfactantsshould be soluble, stable and, preferably, nonfoaming in use. Inasmuchas the solutions herein are alkaline, it is preferred to employ ananionic or nonionic surfactant. Combination of surfactants may beemployed. The term "surfactant", as used herein, may include other formsof dispersing agents or aids. The amounts of surfactant utilized isusually minute, i.e., less than 1000 ppm, but will vary depending on theconditions and the contamination encountered.

The compositions of this invention are preferably free of chelating orcomplexing agents such as high molecular weight acrylic polymers. If thepreferred deionized water is utilized for the saponifier concentrates orsolutions, such chelating and complexing agents are not required.Importantly, since some of the solder joints for the printed circuitboards contain metals such as lead, tin and copper, the absence of achelating agent minimizes the solubility of such metals in thesaponifier solutions during use which could cause environmental problemsduring disposal of the solutions subsequent to use.

The compositions of this invention are characterized by extremely lowenvironmental impact, unlike the chlorinated hydrocarbon solvents andother materials that had been used prior to this invention for printedcircuit board cleaning. The alkali metal carbonate and bicarbonate saltsare naturally occurring and environmentally benign. The saponifiercompositions of the invention have biological oxygen demand (BOD) andchemical oxygen demand (COD) values (as determined by methodshereinafter described more fully) which are well below the acceptablelimits promulgated by various environmental agencies. As described inthe Examples herein, the saponifier compositions, even after use, i.e.,containing the fabrication residues and contaminates, exhibited BODs ofabout 35 and CODs of about 71. In comparison, terpenes, e.g., limonene,are reported as having BODs of about 295 and CODs of about 1,425, (seeHayes et al, U.S. Pat. Nos. 4,640,719 and 4,740,247).

The applicability of the compositions of the invention to variousaspects of the printed circuit/wiring board fabrication process can bestbe understood by a description of a representative assembly process.

The assembly manufacturing process involves the placement of componentssuch as integrated circuits, resistors, capacitors, diodes, etc. on thesurface of the board or their insertion through pre-drilled holes. Thecomponents are then secured by soldering by mechanical or automaticmeans. Interspersed with the soldering operations are cleaningprocedures and inspections to ensure that tape and solder flux residuesthan could lead to premature circuit failure do not remain.

For the removal of rosin soldering flux deposits and other residuesduring printed circuit/wiring board fabrication, the compositions of theinvention may be applied to the boards by immersion in dip tanks or byhand or mechanical brushing. Alternatively, they may be applied by anyof the commercially available printed wiring board cleaning equipment.Dishwasher size units may be employed, or much larger cleaning systemssuch as the "Poly-Clean +" and the various "Hydro-Station" modelsproduced by Hollis Automation, Inc. of Nashua, N.H.

Depending upon their design, these washers may apply the saponifiercompositions of the invention by spraying with mechanical nozzles or byrolling contact with wetted roller surfaces. The temperature at whichthe compositions may be applied can range from room, or ambient,temperature (about 70° F.) to about 180° F., preferably, about 150° to160° F. The saponifier compositions or concentrates are diluted withwater to as low as about 1.0 percent by weight (or volume)concentration.

Once solder flux has been loosened and saponified during a period ofcontact which typically ranges from about 1 to about 5 minutes, thesolutions of the invention are removed. Another advantage of the instantinvention is that the saponifying solutions need not be flushed withsolvents as with the processes of the prior art. Herein, the boards maysimply be flushed with water for a period of up to about 2 minutes.Deionized water is preferred. The optimal rinsing time varies accordingto the kinds of surfactants and the concentrations of the saponifiersolutions used and can easily be determined by routine experimentation.

The cleaned boards are then dried, preferably with forced air. Drying isexpedited if the air is warmed, preferably to above about 100° F.

The efficacy of rosin soldering flux removal from printed wiring boardsis such that the boards meet stringent military specifications for lowresistivity after cleaning. For example, the boards meet theMil-P-28809A standard for low resistivity of the solvent extractsresulting when the contamination has been removed from a circuit boardcleaned according to Mil-P-55110C. The resistivity of such solventextracts after the cleaning of the boards is complete is most easilydetermined with an Omega Meter. Omega Meter is the registered trademarkof Kenco Industries, Inc., Atlanta, Ga., for a microprocessor-controlledcontamination test system that rapidly measures changes in resistivitydue to contaminating ions.

The results of Omega Meter measurements are expressed in equivalentunits of ug NaCl/in² or its metric equivalent. According toMIL-P-28809A, the acceptable resistivity value for a cleaned board isequivalent to 2.2. ug NaCl/cm² or 14 ug NaCl/in², but far better resultsare routinely obtained after solder flux has been removed with thesaponifier solutions of the present invention. A value of about 0.31 ugNaCl/cm², or 2.0 ug NaCl/in², or even less, is typical.

The saponifier solutions of this invention are also effective inremoving other undesirable and deleterious substances and residues. Oneparticularly troublesome substance is the residue left by adhesive tapeused during fabrication of the electronic circuit assemblies.

During the process of gold plating connecting tabs to improve corrosionresistance, tin-lead residues must first be removed from the unplatedtabs. Removal of these residues is carried out through the use ofetching chemicals that can damage other unprotected printedcircuit/wiring board components. To protect vulnerable components fromthe etching chemicals, boards are wrapped on both sides with an adhesiveplating tape which forms a shield or splash guard for all but theexposed tab area. The etching chemicals then remove the tin-leadresidues on the tabs, a nickel plate is applied as a base for the gold,and gold plating of the tabs is finally carried out. The adhesiveplating tape which is maintained in place through all of these etchingand plating steps, is then removed. When the tape is removed followingthe nickel and gold plate step, it is at this point that the saponifiercompositions of the invention may most advantageously be used.

Thus, following removal of the tape, a silicone-based and/orrubber-based adhesive residue may remain on the board. This residue mayeasily be removed by employing the compositions of the invention underthe same conditions described above for solder flux removal. The exactoperational parameters will be determined by the nature of the adhesiveresidue and the tenacity with which it adheres to the board, but theconditions described above are generally effective. As in the case ofsolder flux removal, treatment of the board with the saponifiersolutions of the invention is generally followed by water flushing andair drying.

The efficiency of removal of adhesive residues from printedcircuit/wiring boards by the compositions of the invention is such thatno residues are visible after cleaning. A simple 5-10X stereomicroscopecan facilitate visual inspection for tape residues following cleaning.

The following non-limiting Examples are provided to further illustratethe present invention. All percentages, unless otherwise noted, are byweight. However, due to the near equivalence of the weight and volume ofthe materials utilized, volume percent is essentially the same.

EXAMPLES I-IV

To illustrate the cleaning ability of the saponifier compositions of theinvention, a series of demonstration printed wiring boards were cleanedin a mechanical cleaning system.

The cleaning composition contained, by weight, 75 percent potassiumcarbonate, 12.5 percent sodium bicarbonate, and 12.5 percent sodiumcarbonate monohydrate. Saponifier solutions having variousconcentrations were prepared.

The cleaning system was a "Poly-Clean +" machine which is manufacturedby Hollis Automation, Inc. of Nashua, N.H.

The cleaning sequence comprised the operations of loading, washing,drying, first rinsing, final rinsing and high speed drying carried outin succession. The washing operation utilizing saponifier solutions ofthe invention was done in two stages, i.e., a first regular wash atspray nozzle manifold which directed a regular wash spray at 40 psigfollowed by a "hurricane" spray at 80 psig. The cleaning solutions weremaintained at 160° F. The rinses were also two stage operations; thefirst at 40 psig regular rinse followed by an 80 psig "hurricane" rinsewith the rinse water having a temperature of 160° F. A final rinse waseffected under substantially the same conditions. The circuit boardswere subjected to Alpha air knife drying after the washing and finalrinse stages. In air knife drying, turbine propelled air shears fluidsfrom the boards' surfaces.

Cleaned and dried boards were evaluated for cleaning efficiency bothvisually and by an Alpha 600 5MD Omega Meter resistivity measurements.

The visual test method uses a dyed flux and carrier base injectedbetween glass components and a glass board. This provides excellentaccess for visual inspection. The analysis is further quantified byplacing the board and components against a grid. Each block of the gridis then read as being completely clean or containing residue.

The test method utilizes straight flux and carrier from a rosin mildlyactivated (RMA) flux or paste. It is essentially the solder paste minusthe solder. "Carrier" refers to both the flux paste and all otheradditives included in solder paste, except the solder. This carrier isthen injected with red dye so that visual examination can be made morerapidly. The dye does not affect the carrier density or meltingproperties. The dyed carrier is then injected under the glass componentson specially made test boards. RMA solder paste is not considered anaqueous-compatible flux. The test boards are constructed of glass. A1"×1" square coupon that simulates the component is mounted onto a glasssubstrate. The coupon is glued in place by first laying shim stock ofthe desired standoff height on the glass. Next, the glue is applied andthe coupon set in place until it dries. When dry, the shim stock isremoved. Six coupons are mounted on a single board at 1/2" spacing. Theinterior coupons are further shielded from any nozzles by the firstcoupons in the placement array.

The flux carrier stock is injected under each coupon to entirely fillthe inch-square area. Flux is also added to the area surrounding eachcoupon. The board is IR-reflowed at a typical dwell time of five minutesat reflow temperature. All boards are then stored for 24 hours atambient temperature prior to cleaning. Reflowing and storing increasescleaning difficulty by allowing the board to cool and the flux carrierto set up.

Prior to reflow, the entire area under the coupon is filled with thedyed flux carrier. During reflow, a small percentage of the area underthe coupon develops voids due to expansion and escape of flux volatiles.The area under the coupons filled with baked-on residue is measuredprior to cleaning. The application method causes most of the flux to bebridged across the component standoff height. These regions entirelyfilled with flux are the most difficult to clean. They are also muchless likely to occur in actual manufacturing processes since much lessflux is applied. For the purposes of this test, however, no specialmeasurement qualification is given to this category. By regarding allareas with flux trapped under them as the same, the test method is mademore rigorous. This method is directed toward the measurement ofcleaning effectiveness, which is defined as the percentage of residueremoved. This aqueous cleaning test method is described more fully in apublication by Janet R. Sterritt, "Aqueous Cleaning Power," PrintedCircuit Assembly, September 1989, pp. 26-29.

The results from the cleaning experiments are measured in terms ofcleaning effectiveness as follows. The area of reflowed flux carrier ismeasured prior to cleaning. The test board is then cleaned and theamount of flux residue is visually measured with the aid of a gridpattern. The cleaning effectiveness rating is established by dividingthe area still containing flux after cleaning by the total areacontaining flux prior to cleaning. The measurement technique shows thata completely clean board would result in a cleaning effectiveness ratingof 100%. A test board on which three quarters of the initial residue isremoved would show a 75% reading.

To make the resistivity measurements, cleaned and dried boards wereloaded into a test cell of the instrument and then extracted with acirculating solution of isopropanol:water (25:75), v/v) as specified byMIL-P-55110C and MIL-P-28809A. The resistivity of the solution wasmeasured at a rate of 24 times per minute over a period of about 5-15minutes until equilibrium was reached, indicating that extraction ofboard surface contamination was essentially complete. Equilibrium wasdefined as the point at which the change in measured resistivity of thesolution was less than or equal to 5% of any value measured in theprevious two minutes.

EXAMPLE I

In this example, demonstration glass printed wiring boards (as developedby Hollis Automation to evaluate cleaning solution and as hereinbeforedescribed more fully) which were reflowed with Alpha flux paste asdisclosed above were subjected to the sequence of cleaning operationsalso disclosed above. Five different concentrations of saponifiercleaning solutions, i.e., concentrations of 1.0, 1.7, 2.6, 3.5 and 6.0percent were employed. Three different standoff distances were employed,viz., 2 mils, 6 mils, and 10 mils, respectively.

The results are shown in FIG. 1 in terms of cleaning effectiveness.These results clearly demonstrate the efficacy of the saponifiersolutions of the present invention, especially at concentrations of 2.0percent and above. The efficacy of the saponifier solutions at standoffsas low as 2 mils is especially noteworthy because of the difficulty inaccessing the flux.

EXAMPLE II

Demonstration (H-40) circuit boards (circuit boards produced by HollisAutomation and which ware provided with drilled holes for the passage ofleads therethrough) were immersed in flux and wave soldered with Kester185 and evaluated both visually and on the Alpha 600 5MD Omega Meter forionic contamination. FIGS. 2 and 3 illustrate the results of suchevaluations. The visual evaluation in FIG. 2 again illustrates theeffectiveness of the saponifier solutions of this invention. FIG. 3confirms the visual results by extremely low ionic contaminationresults. FIG. 3 shows a concentration of about 2 percent results in anacceptable resistivity value of about 14 ug NaCl/in² according toMIL-P-28809A. The equilibrium resistivity measurements for the cleaningtests of Example II are also shown in Table I.

                  TABLE I                                                         ______________________________________                                         RESISTIVITY MEASUREMENTS OF CLEANED ROSIN                                    FLUX SOLDERED PRINTED WIRING BOARDS                                                      Saponifier  Equivalent NaCl                                        Test       Concentration                                                                             Contamination                                          Number     (weight %)  (ug/in.sup.2)                                          ______________________________________                                        1          1.0         29.6                                                   2          1.7         16.0                                                   3          2.6         12.0                                                   4          3.5         4.0                                                    5          6.0         1.6                                                    ______________________________________                                    

As shown in Table 1, the saponifier solutions examined were effective atconcentrations below 2.0 percent in producing levels of residual boardsurface contamination that were far below the MIL-P-28809A requirementof 14 ug NaCl/in² equivalent. This is especially noteworthy in view ofthe configuration of the boards subjected to testing.

EXAMPLE III

Demonstration (H-50) circuit boards (produced by Hollis Automation andhaving fewer joints, etc. as the H-40 boards) were wave soldered withKester 185.

Both FIGS. 4 and 5 support the surprising effectiveness of thesaponifier cleaning solutions of the present invention by both visualtesting (FIG. 4) and by Omega Meter testing for ionic contamination(FIG. 5).

Table II also shows the equilibrium resistivity measurements for thecleaning tests of Example III.

                  TABLE II                                                        ______________________________________                                         RESISTIVITY MEASUREMENTS OF CLEANED ROSIN                                    FLUX SOLDERED PRINTED WIRING BOARDS                                                      Saponifier  Equivalent NaCl                                        Test       Concentration                                                                             Contamination                                          Number     (weight %)  (ug/in.sup.2)                                          ______________________________________                                        1          1.7         5.0                                                    2          2.6         3.6                                                    3          3.5         2.4                                                    4          6.0         0.8                                                    ______________________________________                                    

As shown in Table II, the saponifier concentrations examined were alleffective in producing levels of residual board surface contaminationthat were far below the MIL-P-28809A requirement of 14 ug NaCl/in²equivalent.

EXAMPLE IV

In this example, demonstration circuit boards similar to those ofExample III were evaluated again both visually and for ioniccontamination on the Omega Meter. These demo boards were reflowed withKester R-229RMA paste. The results are shown in FIG. 6 which representsthe results from visual testing and FIG. 7 which represents the ioniccontamination results.

The equilibrium resistivity measurements for the cleaning tests effectedin Example IV are also shown in Table III.

                  TABLE III                                                       ______________________________________                                         RESISTIVITY MEASUREMENTS OF CLEANED ROSIN                                    FLUX SOLDERED PRINTED WIRING BOARDS                                                      Saponifier  Equivalent NaCl                                        Test       Concentration                                                                             Contamination                                          Number     (weight %)  (ug/in.sup.2)                                          ______________________________________                                        1          1.7         3.0                                                    2          2.6         0                                                      3          3.5         0                                                      4          6.0         0                                                      ______________________________________                                    

As shown in Table III, again, all the saponifier concentrations examinedwere effective in producing levels of residual board surfacecontamination that were far below the MIL-P-28809A requirement of 14 ugNaCl/in².

EXAMPLE V

For this Example separate tests were performed for effluent chemistryand aluminum abrasion in order to exemplify the environmental efficacyof the saponifiers of this invention. The effluent tests measured pH,BOD and COD. The methods employed are described in the following: (a)for chemical oxygen demand analysis see "Method for the ChemicalAnalysis of Water & Wastes, USEPA 600/4 79 020, Method 410.1 and (b) forbiological oxygen demand analysis see "Method for the Chemical Analysisof Water & Wastes, USEPA 600/4 79 020, Method 405.1.

Two samples were drawn from the wash tank utilized in the previousExamples I-IV. Sample No. 1 was at a concentration of 2.6 percent byweight and Sample No. 2 was at a concentration of 3.5 percent by weight.No additional dilution was made, e.g., by mixing with the rinse waterutilized. Each Sample was also measured for its pH. The results of thesetests and measurements are presented in Table IV.

                  TABLE IV                                                        ______________________________________                                                         Sample Number                                                                 1     2                                                      ______________________________________                                        Concentration (wt %)                                                                             2.6     3.5                                                BOD (ppm)          35      33                                                 COD (ppm)          71      71                                                 pH                 10.51   10.56                                              ______________________________________                                    

The results from the aluminum abrasion test showed no discoloration onthe heat sinks. The evidences no corrosion or other chemical attack ofaluminum surfaces.

The foregoing data clearly indicate the surprisingly low environmentalimpact accruing from the use of the saponifiers of this invention. Theabove BOD and COD values are markedly and, advantageously, lower thanthose required by various federal and/or state environmental agencies.These desirably lower values are also valuable in that costlycontainment equipment and the accompanying processing steps are eithersubstantially reduced or rendered unnecessary.

EXAMPLE VI

This Example describes the methods utilized to attain the biologicaloxygen demand (BOD) and chemical oxygen demand (COD) values ofrepresentative concentrated saponifier solutions of this invention forcomparative purposes with those of the prior art.

Accordingly, samples of a 26 percent saponifier concentrated solution ofthis invention containing, by weight, 75 percent potassium carbonate,12.5 percent sodium bicarbonate and 12.5 percent sodium carbonatemonohydrate and the remainder, i.e., 74 percent, water were prepared andtested according to the USEPA tests 600/4 79 020, methods 410.1 and405.1 utilized in Example V.

The tests resulted in a BOD of less than 12 and a COD of less than 50.These value were reported as such since they were at the lowestthreshold values reproduced by the tests.

These values compare favorably with prior art saponifiers, see forexample, Hayes et al, U.S. Pat. Nos. 4,640,719 and 4,740,247 whereinBODs of about 295 and CODs of about 1,425 are reported.

EXAMPLE VII

This Example reports the pH values obtained from various concentratedsaponifier solutions of the present invention.

In each test procedure the dry ingredients were initially dry mixed andthen 35 percent by weight thereof was added to 65 percent by weight ofdeionized water.

The pH of three different concentrated saponifier solutions were asfollows:

    ______________________________________                                        Saponifier                pH                                                  ______________________________________                                        1.    75 wt % potassium carbonate                                                                           11.15                                                 12.5 wt % sodium bicarbonate                                                  12.5 wt % sodium carbonate monohydrate                                  2.    70 wt % potassium carbonate                                                                           10.80                                                 30 wt % sodium bicarbonate                                              3.    95 wt % potassium carbonate                                                                           11.97                                                 5 wt % sodium bicarbonate                                               ______________________________________                                    

Each of these saponifier concentrates exhibits a pH which isadvantageously compatible with the electronic circuit boards beingcleaned as well as the cleaning equipment presently utilized. Suchsolutions also are not environmentally detrimental and are easilyprocessable and/or recoverable.

EXAMPLE VIII

The procedures of each of Examples I-IV are repeated except that 500 ppmof sodium bisulfite is added to the saponifier solutions as a reducingagent. The demo boards are cleaned consistent with the procedures of theExamples and then are examined as before. Visual testing and Omega Metertesting results are each comparable to the results of the previoustests. Visual examination indicates that the soldered joints remainshiny and are not dulled due to oxidation.

EXAMPLE IX

The procedure of Examples I-IV and VIII are repeated except that 500 ppmof hydrazine hydrate is added to the saponifier solutions as a reducingagent. After cleaning, the demo boards are examined as before. Visualand Omega Meter testing results are comparable to those of the previoustests. Visual examination also indicates that the soldered joints remainshiny. A further benefit accrues in that the hydrazine hydratecompletely dissociates into water and leaves no film or residue.

EXAMPLE X

The procedures of each of Examples I-IV and VIII and IX are repeatedexcept that 0.05 percent by weight of Pluronic L101 is added tosaponifier solutions as an antifoam agent. Pluronic L101 is apoly(oxyethylene) poly(oxypropylene)-poly(oxyethylene) block copolymerhaving a molecular weight of about 3800 and is sold by BASF-Wyandotte.It is noted that any foam resulting from the saponification andagitation of the fluxes and other foam producing residues is reduced.Visual and Omega Meter testing results are comparable to those of theprevious tests.

Many modifications and variations of this invention may be made withoutdeparting from its spirit and scope, as will become apparent to thoseskilled in the art. The specific embodiments described herein areoffered by way of example only, and the invention is limited only by theterms of the appended claims.

We claim:
 1. A saponifier composition for removing rosin soldering fluxand other residues from electronic circuit assemblies and consistingessentially of substantially water soluble components, saidsubstantially water soluble components comprising a mixture ofalkali-metal carbonate and bicarbonate salts and about 6-10 wt. % basedon the composition of a surfactant, said substantially water solublecomponents being free of a chelating agent and so combined that when inan aqueous saponifier solution of from about 1 to 1.7 percent by weightsaid solution has a pH of from about 10 to 12 and an adequate reserve oftitratable alkalinity, at least equivalent to about 0.6 to 4.5 percentcaustic potash when titrated to the colorless phenolphthalein end point.2. The composition of claim 1 wherein said mixture of alkali-metalcarbonate and bicarbonate salts comprise from about 70 to 95 percent byweight alkali metal carbonate salts, and from 5 to 30 percent by weightalkali metal bicarbonate salts, characterized by at least 50 percent byweight of said mixture comprising potassium carbonate.
 3. Thecomposition of claim 2 wherein said mixture comprises about 75 percentweight potassium carbonate, about 12.5 percent by weight sodiumcarbonate monohydrate and about 12.5 percent by weight sodiumbicarbonate.
 4. The composition of claim 1 wherein the saponifiercomposition is in an aqueous concentrated solution comprising from about10 to 45 percent by weight of said saponifier composition and theremainder essentially water.
 5. The composition of claim 4 wherein thesaponifier composition contains an antifoam agent.
 6. The composition ofclaim 1 wherein the saponifier composition is in a solution comprisingfrom about 1 to 1.7 percent by weight of said saponifier composition andthe remainder essentially water.
 7. The composition of claim 6 whereinthe saponifier solution contains up to about 0.1 percent by weight of anantifoam agent.
 8. The composition of claim 6 wherein the saponifiersolution has a biological oxygen demand (BOD) of less than 200 ppm and achemical oxygen demand (COD) of less than 1000 ppm.
 9. The compositionof claim 4 wherein said water is deionized.
 10. The composition of claim6 wherein said water is deionized.